Comparison of N-(3,4,5-tri­meth­oxy­benzyl­idene)naphthalen-1-amine and its reduction product N-(3,4,5-tri­meth­oxy­benzyl)naphthalen-1-amine

The mol­ecules in (E)-N-(3,4,5-tri­meth­oxy­benzyl­idene)naph­thalen-1-amine, C₂₀H₁₉NO₃, (I), and its reduction product N-(3,4,5-tri­meth­oxy­benzyl)naphthalen-1-amine, C₂₀H₂₁NO₃, (II), are both conformationally chiral, but (I) crystallizes in a centrosymmetric space group, while (II) crystallizes with just one conformational enantio­mer in each crystal. A combination of two C—H...O hydrogen bonds links the mol­ecules of (I) into sheets containing a single type of R⁶₆(44) ring, and these sheets are linked into a continuous three-dimensional array by a single π–π stacking inter­action. The mol­ecules of (II) are linked into complex sheets by a combination of N—H...O, C—H...O and C—H...π(arene) hydrogen bonds.

S1. Introduction

We report here the molecular and supra­molecular structures of (E)-N-(3,4,5-tri­meth­oxy­benzyl­idene)naphthalen-1-amine, (I) (Fig. 1), and its reduction product N-(3,4,5-tri­meth­oxy­benzyl)­naphthalen-1-amine, (II) (Fig. 2). Compound (I) was prepared using a thermal condensation reaction between 1-naphthyl­amine and 3,4,5-tri­meth­oxy­benzaldehyde, and (II) was prepared from (I) by reduction with sodium borohydride.

S2. Experimental

S2.1. Synthesis and crystallization

For the synthesis of (I), a mixture of 1-naphthyl­amine (2.1 mmol) and 3,4,5-tri­meth­oxy­benzaldehyde (2.1 mmol) was heated in an oil bath at 423 K for 8 min until complete disappearance of the starting materials, as monitored by thin-layer chromatography (TLC). The mixture was cooled to ambient temperature and the resulting brown solid was triturated with ethanol to afford the title compound, (I), as brown crystals (yield 86%, m.p. 402 K). Spectroscopic analysis: FT–IR (KBr, ν, cm^-1): 3015, 2991, 2953, 2932, 2831, 1618 (C═ N), 1578 (C═C), 1502, 1331, 1227 (C—O), 1130 (C—O), 772.

For the synthesis of (II), a twofold molar excess of sodium borohydride was added in portions over a period of 15 min to a solution of (I) (0.400 g) in ethanol (12 ml). After complete disappearance of the starting compound, (I), as monitored by TLC, the solvent was removed under reduced pressure, an excess of water was added and the product was exhaustively extracted with ethyl acetate. The combined organic extracts were dried using anhydrous sodium sulfate; the drying agent was then removed by filtration and the solvent removed under reduced pressure to afford (II) as pale-yellow crystals (yield 98%, m.p. 412 K). Spectroscopic analysis: FT–IR (KBr, ν, cm^-1): 3413 (N—H), 3004, 2933, 2836, 1586 (C═C), 1532, 1504, 1237 (C—O), 1114 (C—O), 1005, 778.

Crystals of (I) and (II) suitable for single-crystal X-ray diffraction were grown by slow evaporation, at ambient temperature and in air, of the corresponding solutions in methanol.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were located in difference maps, and they were then treated as riding. C-bound H atoms were permitted to ride in geometrically idealized positions, with C—H = 0.95 (aromatic and alkenyl), 0.98 (CH₃) or 0.99 Å (CH₂), and with U_iso(H) = kU_eq(C), where k = 1.5 for the methyl groups, which were permitted to rotate but not to tilt, and k = 1.2 for all other C-bound H atoms. The H atom bonded to atom N1 in (II) was permitted to ride at the position located in a difference map, with U_iso(H) = 1.2U_eq(N), giving an N—H distance of 0.97 Å. Several low-angle reflections, (101) in (I) and (101) and (002) in (II), which had been wholly or partially attenuated by the beam-stop, were omitted from the data sets. In the absence of significant resonant scattering, the Flack x parameter (Flack, 1983) for (II) was indeterminate (Flack & Bernardinelli, 2000); accordingly, the Friedel-equivalent reflections for (II) were merged prior to the final refinements. It was not possible, therefore, to determine the absolute configuration of the molecule in the crystal of (II) selected for data collection. The reference molecule for (II) was selected to have the same sign for the torsion angle C13—C14—O14—C24 as that in the reference molecule for (I).

S3. Results and discussion

Despite their similar molecular constitutions, (I) and (II) crystallize in very different space groups, the centrosymmetric monoclinic space group P2₁/n in the case of (I) and the Sohnke orthorhombic space group P2₁2₁2₁ in the case of (II). Both compounds crystallize with Z = 4 in unit cells of very similar volume, although it is perhaps surprising that the unit-cell volume for (I) is marginally greater than that for (II), presumably reflecting the stronger inter­molecular hydrogen-bonding in (II) (see below). Consistent with this, the density of (I) (1.296 Mg m^-3) is slightly greater than that of (II) (1.283 Mg m^-3).

In neither compound are the ring systems exactly coplanar with the central C—N═C═C linking unit, as indicated by the leading torsion angles (Tables 2 and 3). However, the torsion angles defining the orientation of the tri­meth­oxy­phenyl ring in (I) and of the naphthalene system in (II) with respect to the central spacer unit are both close to zero, but in (I) there is no geometric evidence for any electronic delocalization across the spacer unit. The dihedral angle between the tris­ubstituted aryl ring and the naphthalene system in (I) is 55.4 (2)°, whereas in (II) this angle is 88.2 (2)°. In both compounds, atom C24 of the 4-meth­oxy substituent is considerably displaced from the plane of the adjacent aryl ring, by 1.224 (3) Å in (I) and 1.018 (3) Å in (II). A conformation having atom C24 nearly coplanar with the adjacent aryl ring is precluded by the steric congestion between atom C24 and atoms O13 or O15 which would thereby result. Similar conformations have been observed in other 3,4,5-tri­meth­oxy­phenyl derivatives (Trilleras et al., 2005; Peralta et al., 2007; Cuervo et al., 2009). For compound (II), the torsion angles (Table 3) indicate considerable deviation from planarity for the methyl C atoms, C23 and C25 of the 3-meth­oxy and 5-meth­oxy substituents, which are displaced from the plane of the adjacent ring by 0.252 (3) and 0.468 (3) Å, respectively, as opposed to displacements of only 0.043 (3) and 0.128 (3) Å, respectively, in (I). However, in both compounds the two C—C—O angles at atom C14 have fairly similar values, whereas the corresponding pairs of values at atoms C13 and C15 differ by ca 10° (Tables 2 and 3), as typically found (Seip & Seip, 1973; Ferguson et al., 1996) for meth­oxy­aryl systems in which the meth­oxy C atom is effectively coplanar with the adjacent aryl ring. The N1—C17 distances are clearly consistent with the different oxidation levels in (I) and (II), and it is inter­esting to note the relative values of the bond angles at atoms N1 and C17, but no simple rationalization for this is possible.

The molecules of (I) and (II) exhibit no inter­nal symmetry and hence they are both conformationally chiral. For (I), the centrosymmetric space group accommodates equal numbers of the two conformational enanti­omers. However, for (II), in the absence of any twinning, for which no evidence was found, each crystal contains only a single conformational enanti­omer. It was not possible to establish the absolute configuration of the molecules in the crystal of (II) selected for data collection, but this lack has no chemical significance. Compound (I) thus crystallizes as a conformational racemate, while (II) crystallizes as a conformational conglomerate.

The molecules of (I) are linked into a three-dimensional array in the form of π-stacked hydrogen-bonded sheets. The sheets are built using two C—H···O hydrogen bonds (Table 4) and their formation is readily analysed in terms of two one-dimensional substructures (Ferguson et al., 1998a,b; Gregson et al., 2000). Molecules related by the 2₁ screw axis along (1/4, y, 1/4) are linked by the shorter hydrogen bond to form a C(7) chain (Bernstein et al., 1995) running parallel to the [010] direction (Fig. 3). In addition, molecules related by translation are linked by the longer of the two hydrogen bonds to form a C(11) chain running parallel to the [110] direction (Fig. 4). The combination of chains along [010] and [110] generates a sheet lying parallel to (001) and built from a single type of R⁶₆(44) ring (Fig. 5).

Two sheets of this type, related to one another by inversion, pass through each unit cell, in the domains 0 < z < 1/2 and 1/2 < z < 1.0, respectively, and all of the sheets are linked into a three-dimensional structure by the action of a single aromatic π–π stacking inter­action. The C5–C10 rings in the molecules at (x, y, z) and (2 - x, 1 - y, 1 - z), which lie in different hydrogen-bonded sheets, are strictly parallel, with an inter­planar spacing of 3.480 (2) Å; the ring-centroid separation is 3.798 (2) Å, corresponding to a near-ideal ring-centroid offset of 1.521 (2) Å (Fig. 6). Propagation of this inter­action by the space-group symmetry operators is sufficient to link all of the hydrogen-bonded sheets.

There are four independent hydrogen bonds in the crystal structure of (II) (Table 5), including an N—H···O hydrogen bond, which is necessarily absent from the structure of (I). However, despite the large number of hydrogen bonds in (II), the supra­molecular assembly is only two-dimensional. The overall sheet structure is of considerable complexity but, as in (I), its formation can be analysed in terms of simple substructures. The N—H···O hydrogen bond links molecules related by the 2₁ screw axis along (1/2, y, 1/4) into a C(7) chain running parallel to the [010] direction, and this chain formation is enhanced by a rather long, but nearly linear, C—H···O hydrogen bond which forms a C(5) motif, so that these two inter­actions together generate a C(5)C(7)[R²₂(10)] chain of rings (Fig. 7).

This chain of rings actually lies within a sheet generated by the two C—H···π(arene) hydrogen bonds. The inter­action having atom C4 as the donor links molecules related by translation into a chain running parallel to the [100] direction, while that involving atom C7 as the donor links molecules related by the 2₁ screw axis along (0, y, 1/4) into a chain running parallel to the [010] direction. In combination, these two chains generate a sheet lying parallel to (001) (Fig. 8). Two sheets pass through each unit cell, in the domains 0 < z < 1/2 and 1/2 < z < 1.0, and containing screw axes at z = 1/4 and z = 3/4, respectively. The only possible direction-specific inter­action between molecules in adjacent sheets is a C—H···π(arene) contact (Table 5), which not only involves a C—H bond of low acidity but is characterized by a rather long H···A distance, so that this contact is unlikely to be structurally significant.

Related literature

For related literature, see: Bernstein et al. (1995); Cuervo et al. (2009); Ferguson et al. (1996, 1998a, 1998b); Flack (1983); Flack & Bernardinelli (2000); Gregson et al. (2000); Peralta et al. (2007); Seip & Seip (1973); Trilleras et al. (2005).

Computing details

For both compounds, data collection: COLLECT (Nonius, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures

Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Fig. 2. The molecular structure of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Fig. 3. Part of the crystal structure of (I), showing the formation of a hydrogen-bonded C(7) chain parallel to [010]. Dashed lines indicate hydrogen bonds. For the sake of clarity, H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) or a hash symbol (#) are at the symmetry positions (1/2 - x, 1/2 + y, 1/2 - z) and (1/2 - x, -1/2 + y, 1/2 - z), respectively.

Fig. 4. Part of the crystal structure of (I), showing the formation of a hydrogen-bonded C(11) chain parallel to [110]. Dashed lines indicate hydrogen bonds. For the sake of clarity, H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) or a hash symbol (#) are at the symmetry positions (1 + x, 1 + y, z) and (-1 + x, -1 + y, z), respectively.

Fig. 5. A stereoview of part of the crystal structure of (I), showing the formation of a hydrogen-bonded sheet of R⁶₆(44) rings parallel to (001). Dashed lines indicate hydrogen bonds. For the sake of clarity, H atoms not involved in the motifs shown have been omitted.

Fig. 6. Part of the crystal structure of (I), showing the formation of the π–π stacking interaction which links adjacent hydrogen-bonded sheets. For the sake of clarity, all H atoms have been omitted. The atom marked with an asterisk (*) is at the symmetry position (2 - x, 1 - y, 1 - z).

Fig. 7. Part of the crystal structure of (II) showing the formation of a hydrogen-bonded C(5)C(7)[R²₂(10)] chain of rings parallel to [010]. Dashed lines indicate hydrogen bonds. For the sake of clarity, H atoms not involved in the motif shown have been omitted. Atoms marked with an asterisk (*) or a hash symbol (#) are at the symmetry positions (1 - x, 1/2 + y, 1/2 - z) and (1 - x, -1/2 + y, 1/2 - z), respectively.

Fig. 8. A stereoview of part of the crystal structure of (II), showing the formation of a hydrogen-bonded sheet parallel to (001). Dashed lines indicate hydrogen bonds. For the sake of clarity, H atoms not involved in the motifs shown have been omitted.

(I) (E)-N-(3,4,5-trimethoxybenzylidene)naphthalen-1-amine

Crystal data

C20H19NO3	F(000) = 680
Mr = 321.36	Dx = 1.283 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3821 reflections
a = 8.9697 (11) Å	θ = 2.8–27.5°
b = 9.3300 (9) Å	µ = 0.09 mm^−1
c = 19.9254 (12) Å	T = 120 K
β = 93.846 (8)°	Block, brown
V = 1663.8 (3) Å^3	0.29 × 0.28 × 0.20 mm
Z = 4

Data collection

Bruker Nonius KappaCCD area-detector diffractometer	3820 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	2117 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.070
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.0°
φ and ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −12→12
Tmin = 0.958, Tmax = 0.983	l = −25→25
23021 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.170	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0849P)^2 + 0.2545P] where P = (Fo^2 + 2Fc^2)/3
3820 reflections	(Δ/σ)max = 0.001
220 parameters	Δρmax = 0.29 e Å^−3
0 restraints	Δρmin = −0.28 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.7281 (2)	0.3879 (2)	0.36376 (11)	0.0296 (5)
C2	0.8085 (3)	0.3861 (3)	0.30740 (11)	0.0351 (6)
H2	0.7822	0.3210	0.2719	0.042*
C3	0.9295 (3)	0.4804 (3)	0.30213 (12)	0.0410 (6)
H3	0.9846	0.4779	0.2630	0.049*
C4	0.9690 (3)	0.5751 (3)	0.35213 (13)	0.0407 (6)
H4	1.0496	0.6394	0.3471	0.049*
C5	0.9314 (3)	0.6740 (3)	0.46483 (13)	0.0406 (6)
H5	1.0125	0.7382	0.4608	0.049*
C6	0.8559 (3)	0.6750 (3)	0.52169 (13)	0.0423 (6)
H6	0.8852	0.7391	0.5572	0.051*
C7	0.7341 (3)	0.5814 (3)	0.52824 (12)	0.0384 (6)
H7	0.6812	0.5837	0.5680	0.046*
C8	0.6916 (2)	0.4873 (2)	0.47775 (11)	0.0318 (6)
H8	0.6096	0.4246	0.4827	0.038*
C9	0.7695 (2)	0.4829 (2)	0.41803 (11)	0.0288 (5)
C10	0.8910 (2)	0.5786 (2)	0.41162 (12)	0.0327 (6)
N1	0.6048 (2)	0.2945 (2)	0.37165 (9)	0.0302 (5)
C17	0.5076 (2)	0.2825 (2)	0.32196 (10)	0.0286 (5)
H17	0.5211	0.3358	0.2822	0.034*
C11	0.3764 (2)	0.1899 (2)	0.32425 (10)	0.0281 (5)
C12	0.3613 (2)	0.0951 (2)	0.37753 (10)	0.0286 (5)
H12	0.4385	0.0872	0.4124	0.034*
C13	0.2336 (2)	0.0129 (2)	0.37929 (10)	0.0276 (5)
C14	0.1200 (2)	0.0237 (2)	0.32800 (10)	0.0273 (5)
C15	0.1357 (2)	0.1180 (2)	0.27449 (10)	0.0284 (5)
C16	0.2646 (2)	0.2006 (2)	0.27254 (10)	0.0280 (5)
H16	0.2762	0.2642	0.2360	0.034*
O13	0.20582 (17)	−0.08364 (17)	0.42864 (7)	0.0352 (4)
C23	0.3156 (3)	−0.0947 (3)	0.48375 (11)	0.0377 (6)
H23A	0.4111	−0.1250	0.4671	0.057*
H23B	0.2831	−0.1654	0.5161	0.057*
H23C	0.3281	−0.0012	0.5059	0.057*
O14	−0.00403 (17)	−0.06360 (17)	0.32899 (7)	0.0331 (4)
C24	−0.1241 (3)	−0.0034 (3)	0.36338 (14)	0.0489 (7)
H24A	−0.0885	0.0213	0.4095	0.073*
H24B	−0.2053	−0.0734	0.3644	0.073*
H24C	−0.1607	0.0832	0.3398	0.073*
O15	0.01854 (16)	0.12059 (17)	0.22703 (7)	0.0355 (4)
C25	0.0380 (3)	0.1994 (3)	0.16682 (11)	0.0423 (7)
H25A	0.0487	0.3016	0.1776	0.064*
H25B	−0.0493	0.1853	0.1352	0.064*
H25C	0.1278	0.1655	0.1464	0.064*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0279 (12)	0.0276 (13)	0.0333 (13)	−0.0027 (10)	0.0012 (10)	0.0049 (10)
C2	0.0367 (14)	0.0343 (14)	0.0349 (13)	−0.0023 (11)	0.0059 (11)	0.0018 (10)
C3	0.0388 (15)	0.0436 (16)	0.0423 (15)	−0.0041 (12)	0.0147 (11)	0.0043 (12)
C4	0.0340 (14)	0.0348 (14)	0.0540 (16)	−0.0046 (11)	0.0082 (12)	0.0055 (12)
C5	0.0330 (14)	0.0324 (14)	0.0565 (17)	−0.0066 (11)	0.0037 (12)	−0.0011 (12)
C6	0.0365 (14)	0.0354 (15)	0.0543 (17)	−0.0040 (12)	−0.0015 (12)	−0.0138 (12)
C7	0.0327 (14)	0.0397 (15)	0.0434 (15)	0.0005 (12)	0.0056 (11)	−0.0067 (11)
C8	0.0260 (12)	0.0300 (14)	0.0393 (14)	0.0006 (10)	0.0023 (10)	−0.0016 (10)
C9	0.0236 (12)	0.0271 (13)	0.0356 (13)	0.0006 (10)	0.0011 (10)	0.0046 (10)
C10	0.0274 (13)	0.0279 (13)	0.0428 (14)	−0.0027 (10)	0.0019 (10)	0.0023 (11)
N1	0.0309 (10)	0.0294 (11)	0.0306 (10)	−0.0049 (9)	0.0039 (8)	−0.0005 (8)
C17	0.0341 (13)	0.0264 (13)	0.0258 (12)	−0.0003 (10)	0.0062 (10)	−0.0003 (9)
C11	0.0307 (13)	0.0269 (12)	0.0272 (12)	−0.0019 (10)	0.0057 (9)	−0.0050 (9)
C12	0.0297 (12)	0.0292 (13)	0.0267 (12)	−0.0020 (10)	0.0004 (9)	−0.0018 (9)
C13	0.0328 (13)	0.0252 (12)	0.0250 (12)	−0.0018 (10)	0.0037 (10)	−0.0009 (9)
C14	0.0304 (13)	0.0250 (12)	0.0268 (12)	−0.0033 (10)	0.0039 (9)	−0.0036 (9)
C15	0.0316 (13)	0.0287 (13)	0.0248 (12)	−0.0011 (10)	0.0016 (9)	−0.0050 (9)
C16	0.0341 (13)	0.0250 (12)	0.0254 (12)	−0.0026 (10)	0.0058 (9)	0.0002 (9)
O13	0.0359 (9)	0.0391 (10)	0.0300 (9)	−0.0100 (8)	−0.0018 (7)	0.0084 (7)
C23	0.0414 (14)	0.0425 (16)	0.0285 (13)	−0.0058 (12)	−0.0029 (10)	0.0091 (11)
O14	0.0320 (9)	0.0347 (10)	0.0327 (9)	−0.0064 (7)	0.0029 (7)	−0.0014 (7)
C24	0.0373 (15)	0.0496 (18)	0.0614 (18)	−0.0045 (13)	0.0163 (13)	−0.0060 (13)
O15	0.0356 (9)	0.0386 (10)	0.0313 (9)	−0.0059 (8)	−0.0049 (7)	0.0038 (7)
C25	0.0469 (16)	0.0467 (16)	0.0318 (14)	−0.0095 (13)	−0.0089 (11)	0.0077 (11)

Geometric parameters (Å, º)

C1—C2	1.374 (3)	C11—C12	1.395 (3)
C1—N1	1.425 (3)	C12—C13	1.381 (3)
C1—C9	1.428 (3)	C12—H12	0.9500
C2—C3	1.407 (3)	C13—O13	1.368 (2)
C2—H2	0.9500	C13—C14	1.398 (3)
C3—C4	1.361 (3)	C14—O14	1.380 (2)
C3—H3	0.9500	C14—C15	1.396 (3)
C4—C10	1.417 (3)	C15—O15	1.366 (2)
C4—H4	0.9500	C15—C16	1.392 (3)
C5—C6	1.358 (3)	C16—H16	0.9500
C5—C10	1.412 (3)	O13—C23	1.429 (2)
C5—H5	0.9500	C23—H23A	0.9800
C6—C7	1.412 (3)	C23—H23B	0.9800
C6—H6	0.9500	C23—H23C	0.9800
C7—C8	1.370 (3)	O14—C24	1.429 (3)
C7—H7	0.9500	C24—H24A	0.9800
C8—C9	1.420 (3)	C24—H24B	0.9800
C8—H8	0.9500	C24—H24C	0.9800
C9—C10	1.421 (3)	O15—C25	1.428 (3)
N1—C17	1.280 (2)	C25—H25A	0.9800
C17—C11	1.463 (3)	C25—H25B	0.9800
C17—H17	0.9500	C25—H25C	0.9800
C11—C16	1.393 (3)
C2—C1—N1	122.4 (2)	C13—C12—C11	119.62 (19)
C2—C1—C9	120.2 (2)	C13—C12—H12	120.2
N1—C1—C9	117.40 (19)	C11—C12—H12	120.2
C1—C2—C3	120.2 (2)	O13—C13—C12	125.09 (19)
C1—C2—H2	119.9	O13—C13—C14	114.47 (19)
C3—C2—H2	119.9	C12—C13—C14	120.4 (2)
C4—C3—C2	121.0 (2)	O14—C14—C13	119.71 (19)
C4—C3—H3	119.5	O14—C14—C15	120.35 (18)
C2—C3—H3	119.5	C15—C14—C13	119.9 (2)
C3—C4—C10	120.6 (2)	O15—C15—C14	115.33 (19)
C3—C4—H4	119.7	O15—C15—C16	124.92 (19)
C10—C4—H4	119.7	C16—C15—C14	119.76 (19)
C6—C5—C10	120.9 (2)	C15—C16—C11	119.9 (2)
C6—C5—H5	119.6	C15—C16—H16	120.1
C10—C5—H5	119.6	C11—C16—H16	120.1
C5—C6—C7	120.3 (2)	C13—O13—C23	116.76 (17)
C5—C6—H6	119.8	O13—C23—H23A	109.5
C7—C6—H6	119.8	O13—C23—H23B	109.5
C8—C7—C6	120.5 (2)	H23A—C23—H23B	109.5
C8—C7—H7	119.7	O13—C23—H23C	109.5
C6—C7—H7	119.7	H23A—C23—H23C	109.5
C7—C8—C9	120.3 (2)	H23B—C23—H23C	109.5
C7—C8—H8	119.8	C14—O14—C24	114.13 (17)
C9—C8—H8	119.8	O14—C24—H24A	109.5
C8—C9—C10	118.7 (2)	O14—C24—H24B	109.5
C8—C9—C1	122.3 (2)	H24A—C24—H24B	109.5
C10—C9—C1	118.9 (2)	O14—C24—H24C	109.5
C5—C10—C4	121.8 (2)	H24A—C24—H24C	109.5
C5—C10—C9	119.2 (2)	H24B—C24—H24C	109.5
C4—C10—C9	119.0 (2)	C15—O15—C25	117.36 (17)
C1—N1—C17	117.48 (18)	O15—C25—H25A	109.5
N1—C17—C11	122.34 (19)	O15—C25—H25B	109.5
N1—C17—H17	118.8	H25A—C25—H25B	109.5
C11—C17—H17	118.8	O15—C25—H25C	109.5
C16—C11—C12	120.4 (2)	H25A—C25—H25C	109.5
C16—C11—C17	118.38 (19)	H25B—C25—H25C	109.5
C12—C11—C17	121.17 (19)
N1—C1—C2—C3	−179.9 (2)	N1—C17—C11—C16	169.9 (2)
C9—C1—C2—C3	−1.6 (3)	N1—C17—C11—C12	−8.7 (3)
C1—C2—C3—C4	−0.3 (4)	C16—C11—C12—C13	−0.8 (3)
C2—C3—C4—C10	1.5 (4)	C17—C11—C12—C13	177.7 (2)
C10—C5—C6—C7	−0.7 (4)	C11—C12—C13—O13	179.9 (2)
C5—C6—C7—C8	0.7 (4)	C11—C12—C13—C14	0.2 (3)
C6—C7—C8—C9	−0.1 (4)	O13—C13—C14—O14	−2.5 (3)
C7—C8—C9—C10	−0.5 (3)	C12—C13—C14—O14	177.21 (19)
C7—C8—C9—C1	−179.2 (2)	O13—C13—C14—C15	−179.58 (19)
C2—C1—C9—C8	−179.0 (2)	C12—C13—C14—C15	0.2 (3)
N1—C1—C9—C8	−0.7 (3)	O14—C14—C15—O15	3.0 (3)
C2—C1—C9—C10	2.3 (3)	C13—C14—C15—O15	180.00 (19)
N1—C1—C9—C10	−179.38 (19)	O14—C14—C15—C16	−176.99 (19)
C6—C5—C10—C4	−179.5 (2)	C13—C14—C15—C16	0.0 (3)
C6—C5—C10—C9	0.0 (4)	O15—C15—C16—C11	179.4 (2)
C3—C4—C10—C5	178.8 (2)	C14—C15—C16—C11	−0.6 (3)
C3—C4—C10—C9	−0.8 (4)	C12—C11—C16—C15	1.0 (3)
C8—C9—C10—C5	0.6 (3)	C17—C11—C16—C15	−177.53 (19)
C1—C9—C10—C5	179.3 (2)	C12—C13—O13—C23	2.8 (3)
C8—C9—C10—C4	−179.9 (2)	C14—C13—O13—C23	−177.49 (19)
C1—C9—C10—C4	−1.1 (3)	C15—C14—O14—C24	−92.2 (2)
C2—C1—N1—C17	−46.8 (3)	C13—C14—O14—C24	90.8 (2)
C9—C1—N1—C17	134.9 (2)	C16—C15—O15—C25	8.6 (3)
C1—N1—C17—C11	179.99 (19)	C14—C15—O15—C25	−171.3 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O13^i	0.95	2.52	3.454 (3)	169
C17—H17···O14^ii	0.95	2.40	3.331 (2)	166

Symmetry codes: (i) x+1, y+1, z; (ii) −x+1/2, y+1/2, −z+1/2.

(II) N-(3,4,5-trimethoxybenzyl)naphthalen-1-amine

Crystal data

C20H21NO3	F(000) = 688
Mr = 323.38	Dx = 1.296 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2170 reflections
a = 9.4460 (17) Å	θ = 2.7–27.5°
b = 11.0868 (18) Å	µ = 0.09 mm^−1
c = 15.8195 (16) Å	T = 120 K
V = 1656.7 (4) Å^3	Block, pale yellow
Z = 4	0.41 × 0.39 × 0.32 mm

Data collection

Bruker Nonius KappaCCD area-detector diffractometer	2168 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	1799 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.078
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 2.8°
φ and ω scans	h = −12→12
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −12→14
Tmin = 0.955, Tmax = 0.973	l = −20→16
16040 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.105	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.046P)^2 + 0.4465P] where P = (Fo^2 + 2Fc^2)/3
2168 reflections	(Δ/σ)max = 0.001
220 parameters	Δρmax = 0.21 e Å^−3
0 restraints	Δρmin = −0.18 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.1583 (2)	0.6593 (2)	0.39872 (15)	0.0225 (5)
C2	0.1231 (3)	0.5526 (2)	0.43806 (15)	0.0253 (5)
H2	0.1945	0.5075	0.4662	0.030*
C3	−0.0173 (3)	0.5090 (2)	0.43722 (16)	0.0279 (6)
H3	−0.0385	0.4349	0.4646	0.033*
C4	−0.1232 (3)	0.5712 (2)	0.39793 (16)	0.0280 (5)
H4	−0.2171	0.5405	0.3981	0.034*
C5	−0.1997 (3)	0.7497 (2)	0.31591 (17)	0.0316 (6)
H5	−0.2938	0.7195	0.3145	0.038*
C6	−0.1700 (3)	0.8580 (2)	0.27839 (17)	0.0317 (6)
H6	−0.2430	0.9017	0.2507	0.038*
C7	−0.0316 (3)	0.9049 (2)	0.28072 (17)	0.0311 (6)
H7	−0.0116	0.9808	0.2555	0.037*
C8	0.0740 (3)	0.8412 (2)	0.31924 (16)	0.0282 (6)
H8	0.1670	0.8737	0.3202	0.034*
C9	0.0484 (3)	0.7277 (2)	0.35786 (15)	0.0238 (5)
C10	−0.0924 (3)	0.6816 (2)	0.35684 (16)	0.0252 (5)
N1	0.2942 (2)	0.70652 (18)	0.40028 (13)	0.0251 (4)
H1	0.3276	0.7576	0.3547	0.030*
C17	0.4065 (3)	0.6527 (2)	0.44923 (16)	0.0256 (5)
H17A	0.3703	0.6377	0.5070	0.031*
H17B	0.4843	0.7122	0.4540	0.031*
C11	0.4685 (2)	0.5354 (2)	0.41586 (15)	0.0239 (5)
C12	0.4780 (3)	0.5146 (2)	0.32929 (15)	0.0245 (5)
H12	0.4419	0.5721	0.2903	0.029*
C13	0.5407 (3)	0.4088 (2)	0.30039 (14)	0.0222 (5)
C14	0.5933 (3)	0.3236 (2)	0.35702 (16)	0.0240 (5)
C15	0.5822 (3)	0.3443 (2)	0.44355 (16)	0.0258 (5)
C16	0.5209 (3)	0.4509 (2)	0.47294 (16)	0.0259 (5)
H16	0.5150	0.4659	0.5320	0.031*
O13	0.55711 (19)	0.37999 (15)	0.21667 (11)	0.0282 (4)
C23	0.5280 (3)	0.4733 (2)	0.15638 (16)	0.0334 (6)
H23A	0.4263	0.4908	0.1562	0.050*
H23B	0.5573	0.4465	0.1000	0.050*
H23C	0.5805	0.5463	0.1718	0.050*
O14	0.65142 (19)	0.21920 (15)	0.32366 (11)	0.0299 (4)
C24	0.7927 (3)	0.1905 (3)	0.35080 (17)	0.0333 (6)
H24A	0.8464	0.2652	0.3591	0.050*
H24B	0.8393	0.1410	0.3077	0.050*
H24C	0.7886	0.1456	0.4041	0.050*
O15	0.6316 (2)	0.25456 (17)	0.49517 (12)	0.0350 (5)
C25	0.6763 (3)	0.2872 (3)	0.57782 (16)	0.0371 (7)
H25A	0.7381	0.3580	0.5746	0.056*
H25B	0.7283	0.2199	0.6033	0.056*
H25C	0.5934	0.3062	0.6126	0.056*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0230 (11)	0.0241 (11)	0.0205 (11)	−0.0009 (10)	0.0042 (10)	−0.0034 (10)
C2	0.0277 (12)	0.0264 (12)	0.0219 (12)	0.0015 (10)	0.0010 (10)	−0.0001 (10)
C3	0.0328 (13)	0.0270 (12)	0.0239 (12)	−0.0045 (11)	0.0065 (11)	−0.0023 (11)
C4	0.0235 (12)	0.0310 (13)	0.0294 (13)	−0.0044 (11)	0.0035 (11)	−0.0063 (11)
C5	0.0258 (12)	0.0383 (14)	0.0307 (13)	0.0022 (12)	−0.0006 (11)	−0.0070 (12)
C6	0.0305 (14)	0.0364 (14)	0.0283 (13)	0.0104 (12)	−0.0020 (11)	−0.0035 (12)
C7	0.0381 (15)	0.0269 (13)	0.0282 (13)	0.0065 (12)	0.0060 (12)	0.0018 (11)
C8	0.0285 (13)	0.0276 (12)	0.0286 (13)	0.0028 (11)	0.0048 (11)	−0.0013 (11)
C9	0.0242 (12)	0.0254 (12)	0.0217 (11)	0.0031 (10)	0.0031 (10)	−0.0030 (10)
C10	0.0240 (12)	0.0289 (12)	0.0228 (12)	0.0013 (10)	0.0024 (10)	−0.0069 (11)
N1	0.0225 (9)	0.0227 (10)	0.0301 (11)	−0.0014 (9)	0.0011 (9)	0.0022 (9)
C17	0.0242 (12)	0.0264 (12)	0.0263 (12)	−0.0002 (10)	−0.0010 (10)	−0.0045 (10)
C11	0.0188 (11)	0.0244 (12)	0.0286 (13)	−0.0032 (10)	−0.0004 (10)	−0.0025 (10)
C12	0.0230 (11)	0.0260 (12)	0.0245 (12)	−0.0003 (10)	−0.0013 (10)	0.0034 (10)
C13	0.0214 (12)	0.0257 (12)	0.0195 (11)	−0.0022 (10)	−0.0021 (10)	−0.0008 (9)
C14	0.0232 (11)	0.0197 (11)	0.0292 (12)	−0.0024 (10)	−0.0015 (10)	0.0002 (10)
C15	0.0236 (12)	0.0268 (12)	0.0271 (13)	−0.0033 (10)	−0.0026 (10)	0.0058 (11)
C16	0.0253 (12)	0.0279 (13)	0.0245 (12)	−0.0060 (11)	0.0006 (10)	−0.0014 (10)
O13	0.0355 (10)	0.0274 (9)	0.0219 (9)	0.0075 (8)	−0.0003 (7)	0.0005 (7)
C23	0.0422 (15)	0.0347 (14)	0.0232 (12)	0.0090 (13)	0.0020 (12)	0.0018 (11)
O14	0.0334 (10)	0.0236 (9)	0.0328 (9)	0.0044 (8)	−0.0072 (8)	−0.0024 (8)
C24	0.0308 (13)	0.0341 (14)	0.0350 (14)	0.0086 (12)	−0.0009 (12)	0.0037 (12)
O15	0.0490 (12)	0.0285 (8)	0.0275 (9)	0.0009 (9)	−0.0056 (9)	0.0048 (7)
C25	0.0439 (16)	0.0391 (14)	0.0285 (14)	0.0004 (14)	−0.0068 (12)	0.0074 (12)

Geometric parameters (Å, º)

C1—C2	1.378 (3)	C11—C12	1.392 (3)
C1—N1	1.386 (3)	C11—C16	1.392 (3)
C1—C9	1.440 (3)	C12—C13	1.392 (3)
C2—C3	1.411 (4)	C12—H12	0.9500
C2—H2	0.9500	C13—O13	1.371 (3)
C3—C4	1.364 (4)	C13—C14	1.393 (3)
C3—H3	0.9500	C14—O14	1.385 (3)
C4—C10	1.417 (4)	C14—C15	1.392 (4)
C4—H4	0.9500	C15—O15	1.369 (3)
C5—C6	1.369 (4)	C15—C16	1.396 (4)
C5—C10	1.420 (4)	C16—H16	0.9500
C5—H5	0.9500	O13—C23	1.434 (3)
C6—C7	1.408 (4)	C23—H23A	0.9800
C6—H6	0.9500	C23—H23B	0.9800
C7—C8	1.365 (4)	C23—H23C	0.9800
C7—H7	0.9500	O14—C24	1.437 (3)
C8—C9	1.419 (3)	C24—H24A	0.9800
C8—H8	0.9500	C24—H24B	0.9800
C9—C10	1.425 (3)	C24—H24C	0.9800
N1—C17	1.443 (3)	O15—C25	1.421 (3)
N1—H1	0.9698	C25—H25A	0.9800
C17—C11	1.520 (3)	C25—H25B	0.9800
C17—H17A	0.9900	C25—H25C	0.9800
C17—H17B	0.9900
C2—C1—N1	122.7 (2)	C12—C11—C16	120.3 (2)
C2—C1—C9	118.7 (2)	C12—C11—C17	120.6 (2)
N1—C1—C9	118.5 (2)	C16—C11—C17	119.1 (2)
C1—C2—C3	121.1 (2)	C13—C12—C11	119.4 (2)
C1—C2—H2	119.4	C13—C12—H12	120.3
C3—C2—H2	119.4	C11—C12—H12	120.3
C4—C3—C2	121.4 (2)	O13—C13—C12	124.2 (2)
C4—C3—H3	119.3	O13—C13—C14	115.0 (2)
C2—C3—H3	119.3	C12—C13—C14	120.8 (2)
C3—C4—C10	119.7 (2)	O14—C14—C13	117.6 (2)
C3—C4—H4	120.1	O14—C14—C15	122.8 (2)
C10—C4—H4	120.1	C15—C14—C13	119.6 (2)
C6—C5—C10	121.1 (2)	O15—C15—C14	116.2 (2)
C6—C5—H5	119.4	O15—C15—C16	123.9 (2)
C10—C5—H5	119.4	C14—C15—C16	119.9 (2)
C5—C6—C7	120.2 (2)	C11—C16—C15	120.1 (2)
C5—C6—H6	119.9	C11—C16—H16	120.0
C7—C6—H6	119.9	C15—C16—H16	120.0
C8—C7—C6	119.9 (2)	C13—O13—C23	116.94 (19)
C8—C7—H7	120.0	O13—C23—H23A	109.5
C6—C7—H7	120.0	O13—C23—H23B	109.5
C7—C8—C9	121.7 (2)	H23A—C23—H23B	109.5
C7—C8—H8	119.1	O13—C23—H23C	109.5
C9—C8—H8	119.1	H23A—C23—H23C	109.5
C8—C9—C10	118.2 (2)	H23B—C23—H23C	109.5
C8—C9—C1	122.5 (2)	C14—O14—C24	116.0 (2)
C10—C9—C1	119.3 (2)	O14—C24—H24A	109.5
C4—C10—C5	121.5 (2)	O14—C24—H24B	109.5
C4—C10—C9	119.8 (2)	H24A—C24—H24B	109.5
C5—C10—C9	118.8 (2)	O14—C24—H24C	109.5
C1—N1—C17	122.3 (2)	H24A—C24—H24C	109.5
C1—N1—H1	120.6	H24B—C24—H24C	109.5
C17—N1—H1	113.7	C15—O15—C25	117.7 (2)
N1—C17—C11	116.8 (2)	O15—C25—H25A	109.5
N1—C17—H17A	108.1	O15—C25—H25B	109.5
C11—C17—H17A	108.1	H25A—C25—H25B	109.5
N1—C17—H17B	108.1	O15—C25—H25C	109.5
C11—C17—H17B	108.1	H25A—C25—H25C	109.5
H17A—C17—H17B	107.3	H25B—C25—H25C	109.5
N1—C1—C2—C3	178.1 (2)	N1—C17—C11—C12	33.4 (3)
C9—C1—C2—C3	1.3 (4)	N1—C17—C11—C16	−149.0 (2)
C1—C2—C3—C4	−0.4 (4)	C16—C11—C12—C13	−0.2 (4)
C2—C3—C4—C10	0.1 (4)	C17—C11—C12—C13	177.3 (2)
C10—C5—C6—C7	−0.8 (4)	C11—C12—C13—O13	−179.1 (2)
C5—C6—C7—C8	1.1 (4)	C11—C12—C13—C14	0.3 (4)
C6—C7—C8—C9	−0.2 (4)	O13—C13—C14—O14	−2.0 (3)
C7—C8—C9—C10	−1.0 (4)	C12—C13—C14—O14	178.6 (2)
C7—C8—C9—C1	180.0 (2)	O13—C13—C14—C15	179.9 (2)
C2—C1—C9—C8	177.0 (2)	C12—C13—C14—C15	0.5 (4)
N1—C1—C9—C8	0.1 (3)	O14—C14—C15—O15	−0.3 (4)
C2—C1—C9—C10	−2.0 (3)	C13—C14—C15—O15	177.7 (2)
N1—C1—C9—C10	−179.0 (2)	O14—C14—C15—C16	−179.2 (2)
C3—C4—C10—C5	−179.4 (2)	C13—C14—C15—C16	−1.2 (4)
C3—C4—C10—C9	−0.9 (3)	C12—C11—C16—C15	−0.5 (4)
C6—C5—C10—C4	178.1 (2)	C17—C11—C16—C15	−178.1 (2)
C6—C5—C10—C9	−0.4 (4)	O15—C15—C16—C11	−177.5 (2)
C8—C9—C10—C4	−177.3 (2)	C14—C15—C16—C11	1.3 (4)
C1—C9—C10—C4	1.8 (3)	C12—C13—O13—C23	10.2 (3)
C8—C9—C10—C5	1.3 (3)	C14—C13—O13—C23	−169.2 (2)
C1—C9—C10—C5	−179.6 (2)	C15—C14—O14—C24	−55.7 (3)
C2—C1—N1—C17	−5.3 (4)	C13—C14—O14—C24	126.2 (2)
C9—C1—N1—C17	171.5 (2)	C14—C15—O15—C25	154.8 (2)
C1—N1—C17—C11	73.6 (3)	C16—C15—O15—C25	−26.3 (4)

Hydrogen-bond geometry (Å, º)

Cg1 represents the centroid of the ring C11–C16 and Cg2 represents the centroid of the ring C1–C4/C10/C9.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O13^i	0.97	2.07	3.016 (3)	163
C12—H12···O14^i	0.95	2.59	3.535 (3)	176
C4—H4···Cg1^ii	0.95	2.69	3.632 (3)	173
C7—H7···Cg2^iii	0.95	2.86	3.677 (3)	145

Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) x−1, y, z; (iii) −x, y+1/2, −z+1/2.